Physico-chemical studies of organofluorine compounds: experimental and theoretical approaches

• Grant number: 19/05028-7
• Support Opportunities: Research Grants - Visiting Researcher Grant - International
• Start date: October 12, 2019
• End date: October 26, 2019
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Agreement: CONFAP ; Newton Fund, with FAPESP as a partner institution in Brazil ; UK Academies
• Principal Investigator: Rodrigo Antonio Cormanich
• Grantee: Rodrigo Antonio Cormanich
• Visiting researcher: David O'Hagan
• Visiting researcher institution: University of St Andrews, Scotland
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Associated research grant: 18/03910-1 - Physicochemical studies of fluorinated organic compounds: experimental and theoretical approaches, AP.JP

Abstract

Professor David O'Hagan's (DO'H) primary expertise is in organo-fluorine chemistry as is the main focus of our research, which is being funded by FAPESP through the Young Investigator award (#2018/03910-1); and his deep knowledge on the area will certainly help us to start a new lab in this field that is still incipient in Brazil. So, the visit of Professor DO'H will be extremely important not only to start new collaborative projects, but also to help us to initiate a new, and so far, the first organofluorine lab in Brazil. Organofluorine chemistry is an extremely important area of internationally for the development of fine chemicals, pharmaceuticals and modern materials. We will briefly describe the projects that we plan to collaborate on, in both theoretical and experimental chemistry together with DO'H lab.The scientific programme outlined in this proposal aims to exploit a novel class of organo-fluorine compounds recently developed in St Andrews. The DO'H lab has found that cyclohexane rings, with fluorines arranged around the ring, and with the all cis/syn-stereochemistry, can have extraordinarily polar properties, not the perhaps anticipated hydrophobic properties normally associated with cyclohexanes and increasing levels of fluorination. Their preparation of all cis- tetrafluoro-derivatives and and all cis-hexa- fluorocyclohexane revealed that these compounds are crystalline solids and have unusually high molecular dipole moments for aliphatics. The cyclohexane rings have 'Janus' facial polarity, with a more negative fluorine face and a more positive hydrogen face, an aspect that is not apparent in any current molecular motifs found in organic chemistry. These observations have emerged recently and immediately suggest a novel design concept, using these as building blocks and motifs for introduction into molecular scaffolds as polar moieties and ligands to interact with complementary electrostatic profiles. The proposal aims to explore the potential of this molecular motif with fluorines and extend also to -CF3 and -OCF3, in a variety of arenas, extending from chemical biology to organic materials (liquid crystals). (AU)

Scientific publications

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

PISCELLI, BRUNO A.; SANDERS, WILLIAM; YU, CIHANG; AL MAHARIK, NAWAF; LEBL, THOMAS; CORMANICH, RODRIGO A.; O'HAGAN, DAVID. Fluorine-Induced Pseudo-Anomeric Effects in Methoxycyclohexanes through Electrostatic 1,3-Diaxial Interactions. CHEMISTRY-A EUROPEAN JOURNAL, v. 26, n. 52, AUG 2020. (18/03910-1, 19/05028-7, 19/03855-3)

PISCELLI, BRUNO A.; O'HAGAN, DAVID; CORMANICH, RODRIGO A.. The contribution of non-classical CHaxMIDLINE HORIZONTAL ELLIPSISOC hydrogen bonds to the anomeric effect in fluoro and oxa-methoxycyclohexanes. Physical Chemistry Chemical Physics, v. 23, n. 10, p. 5845-5851, MAR 14 2021. (18/03910-1, 19/03855-3, 19/05028-7)